CO Oxidation Activity of Ag/TiO2 Catalysts Prepared via Oxalate Co-precipitation

Ag/TiO₂ catalysts with different Ag loadings (2, 4, 7 and 10% (w/w)) have been prepared by means of co-precipitation of Ag- and TiO-oxalates followed by temperature programmed oxidation (TPO). The catalysts were subjected to CO oxidation in a flow reactor at atmospheric pressure and temperatures up to 573 K. Best conversion performance was obtained in a CO/O₂ = 1:1 mixture over 10% Ag/TiO₂ for which the temperature of 50% CO conversion was T ₅₀ = 333 K. The initial reaction rates were determined in a circulation reactor at low conversions and apparent activation energies between 13 and 25 kJ/mol were found for all catalysts. Transmission electron microscopy shows a broad range of nano-sized Ag particles on TiO₂ (nearly pure anatase).     

Novel Monocyclam Derivatives as HIV Entry Inhibitors: Design,Synthesis, Anti‐HIV Evaluation,and Their Interaction with the CXCR4 Co‐receptor

The CXCR4 receptor has been shown to interact with the human immunodeficiency virus (HIV) envelope glycoprotein gp120, leading to fusion of viral and cell membranes. Therefore, ligands that can attach to this receptor represent an important class of therapeutic agents against HIV, thus inhibiting the first step in the cycle of viral infection: the virus–cell entry/fusion. Herein we describe the in silico design, synthesis, and biological evaluation of novel monocyclam derivatives as HIV entry inhibitors. In vitro activity testing of these compounds in cell cultures against HIV strains revealed EC₅₀ values in the low micromolar range without cytotoxicity at the concentrations tested. Docking and molecular dynamics simulations were performed to predict the binding interactions between CXCR4 and the novel monocyclam derivatives. A binding mode of these compounds is proposed which is consistent with the main existing site‐directed mutagenesis data on the CXCR4 co‐receptor. Moreover, molecular modeling comparisons were performed between these novel monocyclams, previously reported non‐cyclam compounds from which the monocyclams are derived, and the well‐known AMD3100 bicyclam CXCR4 inhibitors. Our results suggest that these three structurally diverse CXCR4 inhibitors bind to overlapping but not identical amino acid residues in the transmembrane regions of the receptor.     

Synthesis and Cell Growth Inhibitory Activity of Six Non-glycosaminoglycan-Type Heparin-Analogue Trisaccharides

The design and synthesis of heparin mimetics with high anticancer activity but no anticoagulant activity is an important task in medicinal chemistry. Herein, we present the efficient synthesis of five Glc-GlcA-Glc-sequenced and one Glc-IdoA-Glc-sequenced non-glycosaminoglycan, heparin-related trisaccharides with various sulfation/sulfonylation and methylation patterns. The cell growth inhibitory effects of the compounds were tested against four cancerous human cell lines and two non-cancerous cell lines. Two d -glucuronate-containing tetra-O-sulfated, partially methylated trisaccharides displayed remarkable and selective inhibitory effects on the growth of ovary carcinoma (A2780) and melanoma (WM35) cells. Methyl substituents on the glucuronide unit proved to be detrimental, whereas acetyl substituents were beneficial to the cytostatic activity of the sulfated derivatives.     

Spiral-CT-based assessment of tracheal stenoses using 3-D-skeletonization

PURPOSE: Demonstration of a technique for three-dimensional (3-D) assessment of tracheal-stenoses, regarding site, length and degree, based on spiral computed tomography (S-CT). PATIENTS AND METHODS: S-CT scanning and automated segmentation of the laryngo-tracheal tract (LTT) was followed by the extraction of the LTT medial axis using a skeletonization algorithm. Orthogonal to the medial axis the LTT 3-D cross-sectional profile was computed and presented as line charts, where degree and length was obtained. Values for both parameters were compared between 36 patients and 18 normal controls separately. Accuracy and precision was derived from 17 phantom studies. RESULTS: Average degree and length of tracheal stenoses was found to be 60.5% and 4.32 cm in patients compared with minor caliber changes of 8.8% and 2.31 cm in normal controls (p < 0.0001). For the phantoms an excellent correlation between the true and computed 3-D cross-sectional profile was found (p < 0.005) and an accuracy for length and degree measurements of 2.14 mm and 2.53% respectively could be determined. The corresponding figures for the precision were found to be 0.92 mm and 2.56%. CONCLUSION: LTT 3-D cross-sectional profiles permit objective, accurate and precise assessment of LTT caliber changes. Minor LTT caliber changes can be observed even in normals and, in case of an otherwise normal S-CT study, can be regarded as artifacts.     

Sparse on-line gaussian processes

We develop an approach for sparse representations of gaussian process (GP) models (which are Bayesian types of kernel machines) in order to overcome their limitations for large data sets. The method is based on a combination of a Bayesian on-line algorithm, together with a sequential construction of a relevant subsample of the data that fully specifies the prediction of the GP model. By using an appealing parameterization and projection techniques in a reproducing kernel Hilbert space, recursions for the effective parameters and a sparse gaussian approximation of the posterior process are obtained. This allows for both a propagation of predictions and Bayesian error measures. The significance and robustness of our approach are demonstrated on a variety of experiments.     

Chemical fragmentation in quantum mechanical methods

We give a survey on the application of the chemical fragmentation concept in computer modelling of extended covalent systems. It will be stressed that information on molecular topology, as well as location and composition of the reaction centre allows the construction of a reasonable initial guess for the wave function and thus facilitates the solution of the Schr?dinger equation. For systems, where the chemical changes are localised to a few atoms, while others play the role of essentially electrostatic perturbation, a partition into active site and environment is possible providing a background to hybrid quantum mechanical/molecular mechanical (QM/MM) methods. Full molecular orbital treatment of large covalent systems at the minimal basis, semiempirical level becomes possible in the frame of the fragment self-consistent field (FSCF) method which was developed in the past two decades in our laboratory. As an application, we discuss the hydride shift reaction step in xylose isomerase catalysis.     

The influence of cardiac frequency on the hemodynamic consequences of mitral stenosis (author's transl)

In eleven patients with isolated mitral stenosis and regular sinus rhythm a right cardiac catheterization was performed and the wedged pulmonary capillary pressure recorded at rest and during electrical pacing of the right atrium at successive frequencies of 100, 120, 140, and, occasionally, 160 and 180 beats/min, while cardiac output was estimated by the Fick's principle. In all cases a significant elevation of pulmonary capillary pressure with a simultaneous reduction in cardiac output was obtained. The rise of wedged pulmonary pressure was proportional to the increment in cardiac frequency and related also to the calculated area of the mitral valve. The influence of active atrial contraction upon pulmonary pressure and cardiac output is discussed and comparisons with other studies are made. Emphasis is made on the value of atrial pacing as a diagnostic method in mitral stenosis, especially in cases in whom classical effort manoeuvres can not be applied or are insufficient to rise cardiac frequency.     

Estimating the entropy rate of spike trains via Lempel-Ziv complexity

Normalized Lempel-Ziv complexity, which measures the generation rate of new patterns along a digital sequence, is closely related to such important source properties as entropy and compression ratio, but, in contrast to these, it is a property of individual sequences. In this article, we propose to exploit this concept to estimate (or, at least, to bound from below) the entropy of neural discharges (spike trains). The main advantages of this method include fast convergence of the estimator (as supported by numerical simulation) and the fact that there is no need to know the probability law of the process generating the signal. Furthermore, we present numerical and experimental comparisons of the new method against the standard method based on word frequencies, providing evidence that this new approach is an alternative entropy estimator for binned spike trains.     

Atmospheric dry deposition of persistent organic pollutants to the Atlantic and inferences for the global oceans

Atmospheric deposition to the oceans is a key process affecting the global dynamics and sinks of persistent organic pollutants (POPs). A new methodology that combines aerosol remote sensing measurements with measured POP aerosol-phase concentrations is presented to derive dry particulate depositional fluxes of POPs to the oceans. These fluxes are compared with those due to diffusive air-water exchange. For all polychlorinated biphenyl (PCB) congeners and lower chlorinated dibenzo-p-dioxins and furans (PCDD/Fs), air-water exchange dominates the dry deposition mechanism. However, this tendency reverses in some areas, such as in marine aerosol influenced areas and dust outflow regions, consistent with the important variability encountered for the depositional fluxes. Seasonal variability is mainly found in mid-high latitudes, due to the important influence of wind speed enhancing dry deposition fluxes and temperature as a driver of the gas-particle partitioning of POPs. The average dry aerosol deposition flux of sigmaPCBs and sigmaPCDD/Fs to the Atlantic Ocean is calculated to be in the order of 66 ng m(-2) yr(-1) and 9 ng m(-2)yr(-1) respectively. The total dry aerosol deposition of sigmaPCBs and sigmaPCDD/Fs to the Atlantic Ocean is estimated to be 2200 kg yr(-1) and 500 kg yr(-1), respectively, while the net air-water exchange is higher, 22000 kg sigmaPCBs yr(-1) for PCBs and 1300 kg sigmaPCDD/Fs yr(-1). Furthermore, it is suggested that marine aerosol plays an important role in scavenging atmospheric contaminants.     

Determination of linear alkylbenzenesulfonates and their degradation products in soils by liquid chromatography-electrospray-ion trap multiple-stage mass spectrometry

Linear alkylbenzenesulfonates (LAS) (C(10)-C(13)) and their degradation products, sulfophenyl carboxylate compounds (SPCs) (C(2)-C(6), C(8), C(11)), have been extracted from soil samples with methanol, isolated, concentrated by solid-phase extraction, and determined by liquid chromatography/negative ion electrospray quadrupole ion-trap tandem mass spectrometry (MS(n)). The ion fragmentation processes and pathways were studied in detail by MS, MS(2), and MS(3). Upon collision-induced dissociation, the deprotonated molecules of LASs render the ethylene-substituted benzenesulfonate ion (m/z 183), the fragmentation of which gave the intense signal at m/z 119, corresponding to the ethylene-substituted phenoxide ion formed by the loss of sulfur dioxide. The fragmentation pattern of SPCs shows that, for the analytes of large carbon atom chains (>5C), the neutral loss of water is favored whereas for those of short carbon atoms chain, the loss of carbon dioxide is more frequent. Multiple reaction monitoring using isolation only for MS and using isolation and fragmentation for MS(2) and MS(3) were used to identify and quantify each compound. The three MS modes have been validated in terms of sensitivity, selectivity, and precision, showing that each MS stage used reduces sensitivity 10 times. Recoveries from soil were higher than 65% at LOQ level for all the analytes tested, except for C(2)-C(4) SPCs by any MS mode, with relative standard deviation lower than 19%. The utility of the method is demonstrated by successfully quantifying real samples treated with these products. Quantification limits for the methodology developed in this work ranged from 0.5 to 50 microg kg(-1) by MS, from 2 to 400 microg kg(-1) by MS(2), and from 20 to 4000 microg kg(-1) by MS(3). Concentration levels of LASs and SPCs-ranging from 0.1 to 15 mg kg(-1)-were found in soil samples amended with sludges, thus indicating their input and persistence in the soil compartment.